TW493015B

TW493015B - A process for producing carbide particles dispersed in a MCrAly-based coating

Info

Publication number: TW493015B
Application number: TW084106453A
Authority: TW
Inventors: Thomas Alan Taylor; James Kent Knapp
Original assignee: Praxair Technology Inc
Priority date: 1994-06-24
Filing date: 1995-06-23
Publication date: 2002-07-01
Also published as: US5652028A; KR100259481B1; CA2152525C; CN1122377A; EP0688886B1; DE69508658T2; DE69508658D1; CA2152525A1; JP3115512B2; JPH08176786A; KR960001163A; EP0688886A1; CN1065570C

Abstract

A thermal spray process for producing a MCrAlY-based coating wherein M is selected from the group consisting of iron, cobalt, nickel and mixtures thereof and wherein the carbon in the fuel of the thermal spray process converts between 30 to 80 percent by weight of the chromium component in the coating to chromium carbide.

Description

經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（1 ) 本發明係有關一種使用氣體的燃料-氧混合物，在底材表面上熱噴塗一種金屬鉻鋁釔（MOA1Y)基粉末組合物的方法，其中使用含足量碳的燃料混合物，與粉末中的一種或幾種元素反應，形成實質上完全分散於塗層中的碳化物顆粒。在工業上為了各種目的和在各種環境中使用著許多良好的抗氧化和腐蝕的塗料。已經為此目的研製了各種鐵基、鈷基或鎳基超級合金製品，用於如航空，和用作葉 Η、輪葉、封條和用於氣體渦輪發動機的其它部件。在這些應用中，重要的是這些製品對過度氧化和硫化具有足夠的保護，因為這種腐蝕會影響製品的使用壽命而使性能下降及產生可能的安全問題。儘管各種超級合金具有高度的抗蝕性，但是當這些超级合金操作在暴露於高溫環境中時，這種抗蝕性下降。為了增加由合金或超級合金製造的部件的使用壽命，已經研製了各種塗層。開始時是使用鋁化物塗層來提供抗腐蝕外層，但這種塗層受到機槭或熱引發的應變時產生裂縫。另一類研製的塗層是MCr A 1Υ外塗層，其中Μ代表一種過渡金屬元素，如鐵、鈷或鎳。已經發琨這種塗層在延長合金部件在高溫環境中的使用壽命方面，比鋁化物塗層更有效。超級合金底材上之習用MCrAlY塗層之現有問題是，在高溫環境中長時間暴露後，塗層元素與底材元素之間相互擴散。有些底材元素，如钛，已發現經該MCrAlY塗層 -3 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）丨L-------~I (請先閱讀背面之注意事項再填寫本頁) 訂Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493015 A7 B7 V. Description of the Invention (1) The present invention relates to a fuel-oxygen mixture using a gas, and thermally sprays a metal chromium aluminum yttrium (MOA1Y) -based powder on the surface of the substrate. A method of a composition in which a fuel mixture containing a sufficient amount of carbon is used to react with one or more elements in the powder to form carbide particles that are substantially completely dispersed in the coating. Many good anti-oxidation and corrosion coatings are used in industry for various purposes and in various environments. Various iron-, cobalt-, or nickel-based superalloy products have been developed for this purpose, such as in aviation, and as blades, blades, seals, and other components for gas turbine engines. In these applications, it is important that these articles have adequate protection against excessive oxidation and vulcanization, as such corrosion can affect the life of the article, degrade performance and create possible safety issues. Although various superalloys have a high degree of corrosion resistance, when these superalloys are exposed to a high temperature environment, the corrosion resistance decreases. In order to increase the service life of parts made of alloys or superalloys, various coatings have been developed. Initially an aluminide coating was used to provide a corrosion resistant outer layer, but this coating cracked when subjected to organic or thermally induced strain. Another type of coating developed is the MCr A 1Υ outer coating, where M represents a transition metal element such as iron, cobalt or nickel. It has been found that this coating is more effective than the aluminide coating in extending the service life of alloy parts in high temperature environments. A conventional problem with conventional MCrAlY coatings on superalloy substrates is that after prolonged exposure in a high temperature environment, the coating elements and the substrate elements mutually diffuse. Some substrate elements, such as titanium, have been found to be MCrAlY-coated -3-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 丨 L ------- ~ I (Please read first (Notes on the back then fill out this page)

Λ7 Β7 493015 五、發明説明（2 ) 擴散進人外表面氧化物皮中，並使該氧化物皮的保護性下降。因此，需要改進琨行MCrAlY塗層來降低這種相互擴散效應。雖然MCrAlY鼷於對超级合金具有良好抗氧化和抗腐蝕的成功的塗曆之列，但對M C r A 1 Y塗層仍然進行了改良。 (J.S. P.3,993,454號揭示在升高的溫度下，特別適合於鎳和鈷的超级合金物品之保護的塗層。該類塗層的保護性質，是由於在減少氧化/腐蝕的塗層表面形成氧化鋁層。該等塗層含鋁、鉻和選自鎳和鈷之一的一種金屬或其混合物。該等塗層還含有少量限制百分比的給，給可大為改進塗層表面的氧化鋁保護膜的黏附性和耐用性。U.S.P.4,585,481揭示一種類似塗層，只是釔和給與矽一起使用。本發明的目的之一是提供一種製備具有碳化物分散在塗層中的MCrAlY基塗層的熱噴塗方法。本發明的目的之二是提供一種使用爆震槍製備MCrAlY 基塗層的方法，其中該塗層中各處分散有碳化物。本發明的目的之三是提供一種MCrAlY基塗層，其中鉻實質上是以元素鉻形式，少量以碩化鉻的形式存在0 本發明係有關一種製備MCrAlY基塗層的方法，其中Μ 選自鐵、鈷、鎳和其混合物，該方法包括使用如，爆震槍等手段，對底材表面熱嗔塗ΜΟΑ1Υ基粉末組合物，該方法中使用一種氣體燃料-氧化劑混合物，該混合物包括 -4- 本紙張尺度適Μ中國國家標準（CNS ) Λ4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) 、1Τ 經濟部中央標準局員工消費合作社印製經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（3 ) 一種氧化劑和至少一種選自飽和和不飽和烴的可燃氣體，其中氧與碳的原子比在1 . 〇 4 4 : 1和1.00 : 1之間，較佳為1 . 0 2 : 1和1 . 0 0 : 1之間，最佳為約1 , 0 0 : 1 ,在塗層中含有70-100wU碳化物形式的碳組分，較佳含有90-lOOwU 碳化物形式的碳組分，例如C r 23 C 6和/或Cra C 2◦該燃料-氧化劑混合物中的碳，按塗層的重量計，最佳以l-2AtX的量，更佳Μ約2 w t %的量存在於該塗層中。使用爆震槍的爆震手段進行火焰電鍍，可用於製備本發明的塗層。一般地，爆震槍主要由流體冷卻的槍管組成。它有約1英寸內徑。通常將氧和乙炔的混合物與塗料粉末一起進料至槍內。該氧-乙炔燃料氣體混合物點火，產生爆震波，爆震波傳向槍筒下部，由此塗料受加熱並推出槍膛，射向待塗物件。U.S.P.2714563揭示一種利用爆震波於火焰噴塗的方法和設備。該美國專利的說明書內容併於本文作為參考，就好像其全部內容在本說明書中引錄。在某些應用中，可能需要如用氮或氩等惰性氣體稀釋氧-乙炔燃料混合物。已發現這種氣體稀釋麵會降低火焰溫度，雖然它不參加爆震反應。U . S . P . 2 9 7 2 5 5 0握示稀釋氧-乙炔燃料混合物的方法，使所用的爆震電鍍法能增加塗料組分的數目，並賦予可得到的塗層新而更廣闊的應用。該美國專利的說明書併於本文作為參考，就好像其全部內容在本說明書中引錄。在其它應用方面，也可與乙炔一起使用一種第二可燃氣體，這種氣體較佳為丙烯。兩種可燃氣體的應用揭示於美國本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Λ7 Β7 493015 V. Description of the invention (2) Diffusion into the oxide skin on the outer surface of a person, and the protection of the oxide skin is reduced. Therefore, improved MCrAlY coatings are needed to reduce this interdiffusion effect. Although MCrAlY is among the successful coatings that have good oxidation and corrosion resistance to superalloys, the MC R A 1 Y coating is still modified. (JSP3,993,454 discloses coatings that are particularly suitable for the protection of nickel and cobalt superalloy items at elevated temperatures. The protective properties of such coatings are due to the formation of alumina on the coating surface to reduce oxidation / corrosion These coatings contain aluminum, chromium, and a metal selected from one of nickel and cobalt or a mixture thereof. These coatings also contain a small amount of a limited percentage to give an aluminum oxide protective film that can greatly improve the surface of the coating. Adhesion and durability. USP 4,585,481 discloses a similar coating, except that yttrium and silicon are used together. One of the objects of the present invention is to provide a thermal spray for the preparation of MCrAlY-based coatings with carbides dispersed in the coating. Method. Another object of the present invention is to provide a method for preparing an MCrAlY-based coating using a detonation gun, in which carbides are dispersed throughout the coating. A third object of the present invention is to provide an MCrAlY-based coating, wherein Chromium is essentially in the form of elemental chromium and a small amount exists in the form of master chromium. The present invention relates to a method for preparing MCrAlY-based coatings, wherein M is selected from iron, cobalt, nickel and mixtures thereof. The method includes using a method such as a detonation gun to thermally coat the surface of the substrate with a ΜΟΑ1Υ based powder composition. In the method, a gas fuel-oxidant mixture is used. Standard (CNS) Λ4 specification (210 × 297 mm) (Please read the notes on the back before filling this page), 1T Printed by the Employees 'Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed 493015 A7 B7 5 3. Description of the invention (3) An oxidant and at least one combustible gas selected from saturated and unsaturated hydrocarbons, wherein the atomic ratio of oxygen to carbon is between 1.04: 1 and 1.00: 1, preferably 1.0 Between 2: 1 and 1.0 0: 1, preferably about 1, 0 0: 1, the coating contains 70-100 wU of carbon components in the form of carbides, preferably 90-lOOwU of carbides. Carbon components, such as C r 23 C 6 and / or Cra C 2 ◦ The carbon in the fuel-oxidant mixture, based on the weight of the coating, preferably in an amount of 1-2 AtX, more preferably about 2 wt% The amount is present in the coating. It can be used to prepare the coating of the present invention. Generally, a detonation gun is mainly composed of a fluid-cooled barrel. It has an inner diameter of about 1 inch. A mixture of oxygen and acetylene is usually fed into the gun together with the coating powder. The oxy-acetylene fuel gas mixture is ignited to generate a detonation wave, which is transmitted to the lower part of the gun barrel, whereby the coating is heated and pushed out of the gun chamber, and is fired on the object to be coated. USP2714563 discloses a method and method for spraying flames using detonation waves and The contents of the specification of this U.S. patent are incorporated herein by reference as if its entire contents were cited in this specification. In some applications, it may be necessary to dilute the oxygen-acetylene fuel mixture with an inert gas such as nitrogen or argon. This gas-reduced surface has been found to reduce flame temperatures, although it does not participate in the knock response. U.S.P. 2 9 7 2 5 5 0 shows the method of diluting the oxygen-acetylene fuel mixture, so that the knock plating method used can increase the number of coating components and give new and wider coatings available Applications. The specification of this U.S. patent is incorporated herein by reference as if its entire contents were cited in this specification. In other applications, a second flammable gas can also be used with acetylene, and this gas is preferably propylene. The application of two kinds of flammable gas is disclosed in the United States. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)

經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（4 ) 專利4 9 0 2 5 3 9號中，其全部說明書併於本文作為參考，就好像其全部內容在本說明書中引錄。塗層中希望分散有元素鉻和碳化鉻兩者，因為碳化鉻相有助於防止高溫龜裂，元素铬相用於在升高的溫度下給塗層提供良好的抗腐蝕性。咸信塗曆中存在的鉻對塗層中的鋁組分具有協同性效應，它可增加鋁與氧在塗層表面上反應形成A12 〇3時的親合力，所K這將有效而快速地穩定Al2〇3的形成，因而留下過量元素鋁完全分散於塗層中。氣體燃料中增加更多的碳可用於與鉻反應形成碳化鉻，同時保持其量不足，而使元素鉻將仍存在且完全分散於塗層中。一般，期望碳與鉻結合形成〇23C6和/或〇3 C2它使塗層在機械性質方面產生有用而有益的變化。然而，在氧化或硫化環境中，一般是 K元素鉻存在於塗層中為更好。因而，塗層中碳化鉻和鉻的量將取決於使用塗層的特定應用和環境。從氣體燃料中得到的碳量越高，在粉末組合物中可K利用的鉻的百分數越高，就能保證維持有適當量的碳化鉻和元素鉻。向組合物中加入其它元素組分也是可Μ的，這些元素與碳反應具有較高的生成自由能，所Κ這些元素的碳化物可用於增強這些塗層的特性。這些元素的例子可為鈦、組、鎢、鈮、釩和_，且通常實質上形成碳化物，例如90wU或更多進人碳化物相。頃發琨，這些元素碳化物先於C r 23 C 6和/或C r 3 C 2形成，因此添加這些附加元素，更多的鉻將以元素形式保留下來。藉由適當地調本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493015 A7 B7 V. Description of Invention (4) Patent No. 4 9 0 2 5 3 9 The entire specification is incorporated herein by reference, as if its entire contents were cited in this specification record. It is desirable to disperse both elemental chromium and chromium carbide in the coating because the chromium carbide phase helps prevent high temperature cracking, and the elemental chromium phase is used to provide the coating with good corrosion resistance at elevated temperatures. The chromium present in the salt coating has a synergistic effect on the aluminum component in the coating. It can increase the affinity of aluminum and oxygen on the coating surface to form A12 〇3, so this will be effective and fast Stable formation of Al203, leaving excess elemental aluminum completely dispersed in the coating. Adding more carbon to the gaseous fuel can be used to react with chromium to form chromium carbides while keeping the amount inadequate, so that elemental chromium will still be present and fully dispersed in the coating. In general, it is expected that carbon combines with chromium to form 〇23C6 and / or 〇3C2, which results in useful and beneficial changes in the mechanical properties of the coating. However, in oxidizing or sulfurizing environments, it is generally better for K element chromium to be present in the coating. Thus, the amount of chromium carbide and chromium in the coating will depend on the particular application and environment in which the coating is used. The higher the amount of carbon obtained from the gaseous fuel, the higher the percentage of available chromium in the powder composition, and the proper amount of chromium carbide and elemental chromium can be guaranteed to be maintained. It is also possible to add other elemental components to the composition. These elements react with carbon and have a high free energy of formation. The carbides of these elements can be used to enhance the characteristics of these coatings. Examples of these elements may be titanium, titanium, tungsten, niobium, vanadium, and _, and generally form a carbide substantially, such as 90 wU or more into the carbide phase. It turned out that these elemental carbides were formed before C r 23 C 6 and / or C r 3 C 2, so by adding these additional elements, more chromium will remain as an element. By appropriately adjusting the paper size, the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applied (please read the precautions on the back before filling this page)

經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（5 ) 節粉末組合物的組分，就能生產出具有所需鉻和碳化鉻分散劑的塗層，而且如果需要，遷可含有一種或幾種元素碳化物，Μ增強塗層作為特定應用的特性。因此，在熱沉積塗層工藝中使用含碳燃料，可用以製造具有意加入的碳化物相的一類M C r A 1 Υ塗層，Μ進一步控制塗層的機槭和其它性質。金屬原料粉末可與氣體燃料中的碳一起，用於建立塗層中所需碳化物相及所需量的碳化物相。如果需要，粉末組合物中可加入附加組分，Κ優選形成感興趣的碳化物，減少過多的鉻轉化形成碳化鉻。期望含有至少40wU,較佳為40wt!K2於碳化鉻形式之塗層的鉻組分，這樣可賦予塗層附加的機槭強度。至少的鉻應保留在元素鉻相中，這樣該塗層將具有良好的抗腐蝕特性。本發明的一個特點是在MOA1Y基粉末組合物中，可使用更高濃度的鉻，因為一些鉻與燃料混合物中的碳反應形成碳化鉻。發生由氣體燃料-氧化劑和該MCr A 1 Y基粉末組合物生成的碳化物相，這樣，一些鉻將與碳反應，因為鉻在這些組分中具有最高的生成自由能，所Μ鉻將轉化為Cr23C6和/或Cr3C2 。具體而言，至少30-80 wU的鉻將轉化為碳化鉻，較佳為40 -70 wU的鉻轉化為碳化鉻。根據本發明，在該Μ O A 1 Y基粉末組合物中，可使用更高含量的鉻，K補償將形成碳化鉻消耗的鉻量。本發明的塗層可用作為單層的MCr A 1Y基環境塗層，或作為熱障塗層用的加強型黏结塗層。用於本發明中的粉 -Ί - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 493015 A7 B7 V. Description of Invention (5) The components of the powder composition can produce a coating with the required chromium and chromium carbide dispersants, and if necessary, relocate It may contain one or more elemental carbides, and M enhances the characteristics of the coating as a specific application. Therefore, the use of carbonaceous fuels in the thermal deposition coating process can be used to make a type of M C r A 1 Υ coating with intentionally added carbide phase. M further controls the mechanical properties and other properties of the coating. The metal raw material powder can be used with the carbon in the gaseous fuel to establish the required carbide phase and the required amount of carbide phase in the coating. If desired, additional components can be added to the powder composition. K preferably forms carbides of interest and reduces excessive chromium conversion to form chromium carbide. The chromium component of the coating is expected to contain at least 40 wU, preferably 40 wt! K2 in the form of chromium carbide, which can impart additional mechanical strength to the coating. At least chromium should remain in the elemental chromium phase so that the coating will have good corrosion resistance. A feature of the invention is that in MOA1Y-based powder compositions, higher concentrations of chromium can be used because some chromium reacts with carbon in the fuel mixture to form chromium carbide. A carbide phase occurs from the gaseous fuel-oxidant and the MCr A 1 Y-based powder composition. In this way, some chromium will react with carbon because chromium has the highest free energy of formation among these components, and all chromium will be converted. Cr23C6 and / or Cr3C2. Specifically, at least 30-80 wU of chromium will be converted to chromium carbide, preferably 40-70 wU of chromium will be converted to chromium carbide. According to the present invention, a higher content of chromium can be used in the M O A 1 Y-based powder composition, and K compensates for the amount of chromium consumed to form chromium carbide. The coating of the present invention can be used as a single-layer MCr A 1Y-based environmental coating, or as a reinforced adhesion coating for a thermal barrier coating. The powder used in the present invention -Ί-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（6 ) 末較佳為由真空熔融氬霧化法製備的粉末。為了控制將在塗層中形成的碳化鉻的比例，在氣體燃料-氧化劑混合物中氧與碳的原子比可被調節至1 . 0 44 : 1 至1 . 0 0 : 1。在燃料中碳的比例越大，鉻將轉化為碳化鉻的量也就越大。當使用爆震槍技術時，粉末顆粒在槍膛内的時間短，可能不足K在塗層中建立所需的碳化物的平衡分散，因此可能需要熱處理以完成該反應，且因而穩定這些碳化物的形成。該熱處理可在8 0 0勺或Μ上進行，較佳在1 0 0 0 °C或以上進行一段時間以實質上穩定碳化物的形成。加熱步驟的時間可從2到1 0小時，較佳為3至5小時。本發明的MCr/UY粉末組合物含鉻量可為10至較佳15至40wt%，最佳17至，含鋁量可為4至，較佳6至1 8 w t % , 最佳7至1 6 w t ，釔的含量為0 · 1 至 l.OwU，較佳 0.2 至 0.8wU, 最佳 0.2-0.6wU，其餘為鐵、鈷、鍊或其混合物。如果需要，粉末組合物中遷可加入其它組分，如緦、鑭、矽、給、釩、钛、钽、鎢、鈮、锆、鏡、铈或其混合物。其加入量隨加入的目的而改變，但在多數應用中，其量Μ Μ O A 1 Y粉末組合物的重量為基準，Μ 0 . 5至1 0 %，較佳1 - 7 %為宜。適宜的粉末組合物的實例列於表1 。 - 8 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493015 A7 B7 V. Description of Invention (6) The powder is preferably prepared by vacuum melting argon atomization method. To control the proportion of chromium carbide to be formed in the coating, the atomic ratio of oxygen to carbon in the gas fuel-oxidant mixture may be adjusted to 1.044: 1 to 1.00: 1. The greater the proportion of carbon in the fuel, the greater the amount of chromium that will be converted to chromium carbide. When using the detonation gun technology, the time that the powder particles are in the barrel is short and may not be enough to establish the required equilibrium dispersion of carbides in the coating, so heat treatment may be required to complete the reaction and thus stabilize these carbides Formation. This heat treatment may be performed at 800 scoops or M, preferably at 1000 ° C or above for a period of time to substantially stabilize the formation of carbides. The time of the heating step may be from 2 to 10 hours, preferably from 3 to 5 hours. The MCr / UY powder composition of the present invention may have a chromium content of 10 to 15 to 40 wt%, most preferably 17 to 17, an aluminum content of 4 to, preferably 6 to 18 wt%, and most preferably 7 to 1 6 wt. The content of yttrium is from 0.1 to 1.0 wU, preferably from 0.2 to 0.8 wU, and most preferably from 0.2 to 0.6 wU, and the rest is iron, cobalt, chains or mixtures thereof. If desired, other components such as hafnium, lanthanum, silicon, vanadium, titanium, tantalum, tungsten, niobium, zirconium, mirrors, cerium, or mixtures thereof may be added to the powder composition. The amount of addition varies depending on the purpose of addition, but in most applications, the amount of ΜOMAl Y powder composition is based on the weight, preferably from M0. 5 to 10%, preferably from 1 to 7%. Examples of suitable powder compositions are listed in Table 1. -8-This paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)

493015 A7 B7 五、發明説明（7 ) 經濟部中央標準局員工消費合作社印製表1 元素-組合物的重量百分數組合物 Co Νί Cr A1 Y Ta Nb NiCrAlY — 餘量 15-25 7-14 0.1-1 CoCrAlY 餘量 -- 10-50 4-12 0.1-1 NiCoCrAlY 10 - 40 餘量 17-30 7-16 0.H NiCoCrAlYHb 10 - 40 餘量 17 - 30 4-16 - 0.1-1 2-8 CoCrAlYTa 30-83 一 10 - 50 4-12 0.1-1 1-5 NiCrAlYTa — 47-72 15-25 7-14 0.1-1 1-5 —：-------— (請先閱讀背面之注意事項再填寫本頁) 訂493015 A7 B7 V. Description of the invention (7) Table 1 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy Element 1-Composition by weight% Composition Co Ν Cr A1 Y Ta Nb NiCrAlY — balance 15-25 7-14 0.1- 1 CoCrAlY balance-10-50 4-12 0.1-1 NiCoCrAlY 10-40 balance 17-30 7-16 0.H NiCoCrAlYHb 10-40 balance 17-30 4-16-0.1-1 2-8 CoCrAlYTa 30-83 a 10-50 4-12 0.1-1 1-5 NiCrAlYTa — 47-72 15-25 7-14 0.1-1 1-5 —: -------— (Please read the note on the back first (Please fill in this page again)

本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（8 ) 本發明所用的氣體燃料-氧化劑混合物的可燃氣體，可以是至少一種選自下列氣體的氣體：乙炔（C 2 Η 2 )、丙炔（C3 Ηβ )、甲烷（CH4 )、甲基乙炔（c3 Η4 )、丙烷 (C3 Η8 )、乙烷（C2 Η6 )、丁二烯（C4 Η6 )、丁烯 iC4 Hs )、丁烷（C4 Η10)、環丙烷（C3 Η6 )、丙二烯 (C3 H4 )、環丁烷（C4 H8 )和環氧乙烷（C2 H4 0)。較佳的燃料混合物包括單純乙炔氣，或它與至少一種可燃氣體如丙炔等的混合物。如果需要，一種惰性氣體，如氮氣可K加到氣體燃料混合物中，加入量按可燃燃料和氧氣的體積計，為2 0至 5 0體積％，較佳30至40體積％。使用爆震槍時，氣體燃料-氧化劑混合物的流速可在10至14英尺3 /分，較佳 11至13英尺3 /分之間改變，點火速度可在每秒鐘4至 1 0次，較佳7至9次之間改變。槍筒中粉末加料速度為 5至35克/分，較佳15至25克/分之間改變。這些參數的選擇是使所需的碳量可與鉻反應，使最終塗層中生成所需量的碳化鉻。製備本發明的塗層的另一方法可Μ是用高速氧-燃料，包括所謂的超音火焰噴塗塗佈法。在這些方法中，氧和一種燃料氣體連續燃燒，因而形成一種高速氣流，向該氣流中注入塗層組合物的粉末材料。粉末顆粒被加熱至接近於熔點，被加速並衝向待塗佈表面。通過撞擊，粉末顆粒向外流動，形成相互覆蓋的、薄的透鏡狀顆粒和突起。當使用含碳型燃料進行高速氧-燃料技術於沉 —10— 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 493015 A7 B7 V. Description of the invention (8) Combustible gas of gaseous fuel-oxidant mixture used in the present invention Can be at least one gas selected from the group consisting of acetylene (C 2 Η 2), propyne (C 3 Η β), methane (CH 4), methyl acetylene (c 3 Η 4), propane (C 3 Η 8), and ethane (C 2 Η6), butadiene (C4 Η6), butene iC4 Hs), butane (C4 Η10), cyclopropane (C3 Η6), propadiene (C3 H4), cyclobutane (C4 H8), and ethylene oxide Alkane (C2 H4 0). Preferred fuel mixtures include pure acetylene gas, or a mixture with at least one combustible gas such as propyne. If necessary, an inert gas such as nitrogen may be added to the gaseous fuel mixture in an amount of 20 to 50% by volume, preferably 30 to 40% by volume based on the volume of the combustible fuel and oxygen. When a detonation gun is used, the flow rate of the gas fuel-oxidant mixture can be varied between 10 and 14 feet 3 / minute, preferably between 11 and 13 feet 3 / minute, and the ignition speed can be 4 to 10 times per second. Better change between 7 and 9 times. The powder feed rate in the barrel is varied from 5 to 35 g / min, preferably between 15 and 25 g / min. These parameters are chosen so that the required amount of carbon can react with chromium to produce the required amount of chromium carbide in the final coating. Another method for preparing the coatings of the present invention may be using high-speed oxy-fuels, including the so-called supersonic flame spray coating method. In these methods, oxygen and a fuel gas are continuously burned to form a high-speed gas stream into which the powdered material of the coating composition is injected. The powder particles are heated to a temperature close to the melting point, accelerated and rushed toward the surface to be coated. By impact, the powder particles flow outward, forming thin, lenticular particles and protrusions that cover each other. When using carbonaceous fuel for high-speed oxygen-fuel technology in Shen —10— This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

493015 經濟部中央標準局員工消費合作社印製末不漿A1的，，t%經 $ 可 Γ W 氧粉生電 C 備量外 Ο 已。層的產的CO製含此 5 。卜塗同，蔽Ni末鋁。的。}40漿相氣屏之粉屬量入合 W 約電由合氩物的金鋁加结 ί、高本，混軸成量的屬明性量的基法烯同。組鋁耗金發活測層與方丙有層示加消餘本行了塗有槍和具塗所附鋁殘據進行漿具震氧用本中含化的根碳進電層爆的使基 2 用氧等有的度本塗用變由的表是為相含法硬基槍是可是較從層化致中方觀比震丨例層比是塗轉大末槍微度爆 β 比塗為層槍充曆粉震氏硬， ¾用種作塗震補塗的爆維的示 (Α使三用燈爆 Μ 漿層自的層顯層中第，噴。用電塗來層塗果塗其。的漿的是與槍與塗槍結種，比備電備鋁生震來類震的兩的碳製等製加產爆用這爆驗頭造氧燈該末附而於，對現試製同噴粉，因用Nb發化 A7 B7 五、發明説明（9 ) 積該塗層時，Μ英尺3 /小時表示的氧氣與燃料之比應為低氧比，該比例為4 : 1至1 : 1，較佳為3 : 1至2 : 1。本發明的塗層材料非常適合於塗佈由如鈦、鋼、鋁、鎳、鈷、它們的合金等製成的底材。實例1 在ΙΝ718基稈上製備三種塗層，在1975Τ在真空中熱處理4小時，磨平，並受噴砂處理。每種塗層的樣品在 2 0 0 0 °F下受到循環氧化試驗，在這些試驗中，樣品在熱區放置5 0分鐘，然後取出冷卻1 0分鐘。經此試驗後，截取稈的橫截面，黏貼在環氧樹脂上並磨光，顯現出表面氧化物曆和其下方的鋁化物貧化層的情況。本紙張尺度適用中國國家標準（CNS ) A4規格（210ΧΓ2妁公釐） (請先閱讀背面之注意事項再填寫本頁)493015 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, A1, t% via $ can Γ W oxygen powder power generation C is out of reserve 〇 Already. The layered CO system contains this 5. Bu Tu The same, shielding Ni and aluminum. of . The powder content of the 40-phase slurry gas shield is equal to W. The electricity is combined with gold and aluminum of the argon compound, which is high, and the mixed axis content is the same as the clear amount of base farene. Group aluminum consumption test layer and square C layer have been added. The bank used guns and aluminum residues attached to the paste to vibrate oxygen. The base carbon contained in the book was used to explode the base. 2 The degree of use of oxygen and other coatings is shown in the table. The hard base gun is a phase-contained method, but it is more stratified and caused by the Chinese side. The layer gun is filled with powder shock, and the explosion dimension is shown by using a seed as a supplementary coating (A makes the three lamps explode, and the slurry layer is the second most visible layer in the spray layer. Spray. Use electric coating to coat the fruit. The slurry is a combination of a gun and a coating gun, and two carbon systems, such as an electric shock generator and an aluminum shock generator, are used to produce explosions. The explosion test head oxygen generating lamp should not be attached. Trial production of the same powder, because the use of Nb chemical A7 B7 V. Description of the invention (9) When the coating is accumulated, the ratio of oxygen to fuel expressed in ft3 / h should be a low oxygen ratio, which is 4: 1 to 1: 1, preferably 3: 1 to 2: 1. The coating material of the present invention is very suitable for coating substrates made of, for example, titanium, steel, aluminum, nickel, cobalt, their alloys, etc. Example 1 Three coatings were prepared on the IN718 base stalk, 1975T was heat treated in vacuum for 4 hours, flattened, and sandblasted. Samples of each coating were subjected to a cyclic oxidation test at 2000 ° F. In these tests, the samples were placed in a hot zone for 50 minutes, and then Take out and cool for 10 minutes. After this test, the cross section of the stalk is cut, adhered to the epoxy resin and polished, showing the surface oxide calendar and the depleted layer of aluminide below it. This paper scale applies to China National Standard (CNS) A4 Specification (210 × Γ2 妁 mm) (Please read the precautions on the back before filling this page)

493015 A7 B7 五、發明説明（10 ) 比較但略差的抗氧化性。因此，對於必須考慮高硬度和高抗氧化性兩者的應用而言，例如在抗腐蝕磨損的渦輪葉Η Z形槽口塗佈或在高溫環境中抗蠕變塗佈應用的場合，爆震槍塗層應為優於習用的電漿體塗層，因為它提供碳Κ形成分散在整個塗層中的碳化物。表2 外部鋁化物貧化區及氧化皮的平均厚度（密耳）爆震槍塗層* 氧碳比塗層硬度 HV 3 2000°F 80小時 160小時 A 1.00:1 602 0.51 0.91 B 1·03:1 586 0.53 0.81 電漿 — 431 0.45 0.61 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 對於塗層Α和Β的起始粉末組成，K : 21.8Co-16.9Cr- 14·2Α1 -0·65Υ-5Nb-餘量 Νί 對於電漿塗層的起始粉末組成，按¥〇計： 21.8Co-17.2Cr-12.5Α卜0.6Υ-餘量 Ni 實例2 _12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（11 ) 化學分析實例1的兩種爆震槍塗層的氧和碳含量，结果列於表3 。此外，具有示於表3中之碳對氧比之兩種爆震槍塗層是由相似組成的粉末製得，只是沒有加入鈮，對這些塗層C和D也進行了類似的化學分析。一種基本電漿噴燈塗層E由相似但鋁含量較低的NiCoCrAlY粉末製備，也對其進行了化學分析。根據化學分析的结果，計算了這些塗層中各不同相的量。其中假定氧形成平衡量的最穩定的氧化物，即形成Y 2 0 3 ,及部分A 1 2 0 3 。假定碳首先形成最穩定的碳化物，N b C ,然後是部分 Cr 3 C 2 。這些計算總結在表3中。頃發琨，當N b加到起始粉末中時，該計算顯示塗層中形成的C r 3 C 2量相應減少，因而殘餘的金屬鉻量增加。當氧碳比增加時，對於在這些塗層中得到碳的範圍而言，A 1 2 〇 3的量增加，C r 3 C 2的量減少，N b C的量保持不變（見塗層A和B )。殘餘金屬鉻的量因此可藉由加入的金屬元素Μ的量來控制，其中Μ是一種強MC型碳化物的形成者，且另外受到塗相Ϊ方法中氧碳比的控制。而且，分散的氧化物與分散的碳化物相之比，受塗佈方法中氧碳比的控制，同時在賁例1中所示1.00:1至1.03:1的範圍內的塗層，在較寬的範圍内具有相似的硬度和抗氧化性。因此塗佈過程的條件可依據所打算的應用來進行選擇，使得到所希望的更高的碳化物分散狀態。頃發琨，含N b塗層Α和Β實質上比基本電漿塗層更硬 -13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)493015 A7 B7 5. Description of the invention (10) Comparative but slightly inferior oxidation resistance. Therefore, for applications where both high hardness and high oxidation resistance must be considered, such as in the application of corrosion-resistant turbine blade 的 Z-notch coating or creep coating application in high temperature environments, knocking The gun coating should be superior to the conventional plasma coating because it provides carbon K to form carbides dispersed throughout the coating. Table 2 Average thickness of outer aluminum depleted area and scale (mil) Detonation gun coating * Oxygen-carbon ratio coating hardness HV 3 2000 ° F 80 hours 160 hours A 1.00: 1 602 0.51 0.91 B 1.03 : 1 586 0.53 0.81 Plasma — 431 0.45 0.61 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) For the starting powder composition of coatings A and B, K: 21.8Co -16.9Cr- 14 · 2Α1 -0 · 65Υ-5Nb- remainder Nί For the starting powder composition of the plasma coating, calculated as ¥ 〇: 21.8Co-17.2Cr-12.5Αb 0.6Υ- remainder Ni Example 2 _12- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 493015 A7 B7 V. Description of the invention (11) Two types of detonation guns for chemical analysis example 1 The oxygen and carbon contents of the coatings are shown in Table 3. In addition, the two detonation gun coatings with the carbon-to-oxygen ratio shown in Table 3 were made from powders of similar composition except that no niobium was added, and similar chemical analyses were performed on these coatings C and D. A basic plasma torch coating E was prepared from similar NiCoCrAlY powder with low aluminum content, and chemical analysis was also performed. Based on the results of chemical analysis, the amounts of different phases in these coatings were calculated. It is assumed that oxygen forms the most stable oxide in terms of level, that is, Y 2 0 3, and part A 1 2 0 3. It is assumed that the carbon first forms the most stable carbide, N b C, and then a portion of Cr 3 C 2. These calculations are summarized in Table 3. After a while, when Nb was added to the starting powder, the calculation showed that the amount of Cr3C2 formed in the coating decreased correspondingly, and thus the amount of residual metallic chromium increased. As the oxygen-to-carbon ratio increases, for the range of carbon obtained in these coatings, the amount of A 1 2 0 3 increases, the amount of C r 3 C 2 decreases, and the amount of N b C remains unchanged (see coatings). A and B). The amount of residual metallic chromium can therefore be controlled by the amount of metal element M added, where M is the former of a strong MC-type carbide and is additionally controlled by the oxygen-carbon ratio in the coating phase method. Moreover, the ratio of the dispersed oxide to the dispersed carbide phase is controlled by the oxygen-to-carbon ratio in the coating method, and the coating in the range of 1.00: 1 to 1.03: 1 shown in Example 1 is relatively It has similar hardness and oxidation resistance over a wide range. Therefore, the conditions of the coating process can be selected according to the intended application, so as to achieve the desired higher carbide dispersion state. It ’s a hairpin, with Nb coatings A and B that are substantially harder than basic plasma coatings. -13- This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back first) (Fill in this page again)

經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（l2 ) ，如表2所示。此外，不含N b的塗層（塗層C和D )被發琨兩者的硬度均為約5 5 0 Η V 3 。因此，N b的另一作用是增加塗層的硬度，這在需要高硬度、抗蠕變或耐高溫強度的塗層的應用中，預料是有益的。MC碳化物，如NbC 的應用，預料比在簡單的N i C 〇 C r A 1 Y爆震槍塗層中的 C r 3 C 3或更低級的碳化鉻在塗佈溶液方面具有更優的高溫穩定性。 -14- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493015 A7 B7 V. Description of the Invention (l2), as shown in Table 2. In addition, the coatings (coatings C and D) that did not contain N b were subjected to a hardness of about 5 50 Η V 3. Therefore, another effect of Nb is to increase the hardness of the coating, which is expected to be beneficial in applications requiring a coating with high hardness, creep resistance, or high temperature resistance. MC carbides, such as NbC applications, are expected to have better coating solutions than C r 3 C 3 or lower chromium carbides in simple Ni C 0 C r A 1 Y detonation gun coatings. High temperature stability. -14- This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297mm) (Please read the precautions on the back before filling this page)

493015 A7 B7 五、發明説明（l3 蹿筇_画3>fuBsffi誃缪汫薛a,^__nH^i+: 21 · 8COI16 · 9Cr-14.2 ATP 65 γ—50-難 _ Νί; iicfaD : 12^200-170114,2^10.77^13:::¾ iffiE: 21oocoll7,2crllr°5Allo.6YI^_Ni。經濟部中央標準局員工消費合作社印製 A D-Gun B D-Gun C D-Gun 1) D-Gun E電漿塗層 1.00：1 1,25 2.04 1,03:1 1,55 1.45 1.00：1 1.26 1.95 1.03:1 1.77 1,38 --- 0·15 0.01 1 s n m m 測得值wt% -fef TJM LL· 1.20 4.00 5,10 10.90 1.20 5,20 5.10 6.30 1.30 4,00 0.00 15.30 1.30 5.90 0.00 10.80 1.30 0.00 0.00 o.io Y 2 〇 3 A1 2 0 3 HbC Cr 3 C 2 計算值Vo 1.% — 一 — — 一 to 一 — 一 to cn 00 Hpa. ·<! ΓΟ 〇〇〇〇〇 h~* H-i -<1 -*<1 00 H-* r〇 <L71 ^ 05 05 〇〇〇〇〇 0 計算值wU 紲3 jj — (請先閱讀背面之注意事項再填寫本頁) 訂 4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）經濟部中央標準局員工消費合作社印製 493015 A7 B7 五、發明説明（l4 ) 應當理解，在不偏離本發明的精神和範圍的情況下，對於這裡所示和描述的較佳具體實例可作出許多修改和變化。例如，本發明的塗層上遷可K塗上氧化锆的頂塗層，製備性能良好的雙重熱障塗層。 —16— 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)493015 A7 B7 V. Description of the invention (l3 蹿筇 _ 画 3 > fuBsffi 誃缪誃薛 a, ^ __ nH ^ i +: 21 · 8COI16 · 9Cr-14.2 ATP 65 γ-50-difficult _ Ιί; iicfaD: 12 ^ 200- 170114,2 ^ 10.77 ^ 13 ::: ¾ iffiE: 21oocoll7,2crllr ° 5Allo.6YI ^ _Ni. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A D-Gun B D-Gun C D-Gun 1) D-Gun E Plasma coating 1.00: 1 1,25 2.04 1,03: 1 1,55 1.45 1.00: 1 1.26 1.95 1.03: 1 1.77 1,38 --- 0 · 15 0.01 1 snmm Measured value wt% -fef TJM LL · 1.20 4.00 5,10 10.90 1.20 5,20 5.10 6.30 1.30 4,00 0.00 15.30 1.30 5.90 0.00 10.80 1.30 0.00 0.00 o.io Y 2 〇3 A1 2 0 3 HbC Cr 3 C 2 Calculated Vo 1.% — One — one to one — one to cn 00 Hpa. · &Lt;! ΓΟ 〇〇〇〇〇〇h ~ * Hi-< 1-* < 1 00 H- * r〇 < L71 ^ 05 05 〇〇〇〇〇0 Calculated value wU 绁 3 jj — (Please read the notes on the back before filling out this page) Order 4 This paper size applies to China National Standard (CNS) A4 (210X297 mm) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative 493015 A7 B7 V. Description of invention (l4) , Without departing from the spirit and scope of the present invention, for the preferred specific examples shown and described herein, many modifications and variations may be made. For example, the coating of the present invention can be coated with a top coating of zirconia to prepare a dual thermal barrier coating with good performance. —16— This paper size is applicable to China National Standard (CNS) A4 (210X 297mm) (Please read the precautions on the back before filling this page)

Claims

申請專利範圍Patent application scope

A8 B8 C8 D8 公告本第84106453號「一種製備分散在金屬鉻鋁釔基塗層中的碳化物顆粒的方法」專利案（87年11月修正）杰申請專利範圍 (請先閲讀背面之注意事項再填寫本頁) 1· 一種製備Μ選自鐵、鈷、鎳和其混合物的MCrA1Y基之抗氧化及腐蝕塗層的方法，其係包括使用一種氣體燃料-氣化劑混合物藉由爆震槍裝置，將MCrA 1Y基粉末組合物熱噴塗到底材表面，該氣髏燃料-氧化劑混合物包括一種氧化劑和至少一種選自飽和和不飽和烴的可燃氣體，其中氣與碩的原子比為1.044:1至1州0:1; 及其中氣體燃料-氣化劑中之碩偽於足以將30-80重量S：於塗層中之鉻成份轉化為碩化鉻；及該碩存在於至少該塗層之1重量％。 2·如申請專利範圍第1項的方法，其中已塗覆底材被加熱到800TC以上溫度，加熱時間足以穩定燃料-氧化劑混合物中的碩與粉末組合物中的鉻之反應，生成所需量的磺化鉻。經濟部中央標準局員工消費合作社印製 3·如申請專利範圍第1項的方法，其中的MCrAlY基粉末組合物進一步包含至少一種選自銪、鑭、矽、姶、鉅、鎢、鈦、锆、鈽、鈮、钒和鐙中之元素。 4.如申請專利範圍第1項的方法，其中的可燃氣體是乙炔和丙烯的混合物；氧與磺的原子比為1·02:1至1·00 :1,塗層中的40-80重量的鉻組分是磺化鉻。 -1- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 493015 A8 B8 C8 D8 六、申請專利範圍 5. —種製備Μ選自鐵、鈷、鎳和其混合物的MCrAlY基之抗氣化及腐蝕塗層的方法，其俗包括使用一種氣體燃料-氣化劑混合物藉由高速氣燃料裝置，將MCrAlY 基粉末組合物熱噴塗到底材表面，該氣體燃料-氣化劑混合物包括一種氧化劑和至少一種選自飽和和不飽和烴的可燃氣體，其中氧與燃料的比例，按立方英尺/ 小時計為4:1至1:1 ,塗層中含30 -7 5重量S；的於碩化鉻形式之鉻組成。 6. 如申請專利範圍第5項的方法，其中經塗覆底材被加熱到800 ¾以上溫度，加熱時間足以穩定燃料-氣化劑混合物中的磺與粉末組合物中的鉻之反應，生成所需量的碳化鉻。 7. 如申請專利範圍第5項的方法，其中的MCrAlY基粉末組合物還含有至少一種選自銪、鑭、矽、姶、鉅、結、鎢、钒、鈽、鈮和鏡中之元素。經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 8. —種塗覆以包括MCrAlY基材料的熱噴塗層的底材，其中Μ選自鐵、鈷、鎳和其混合物，其中30-80重量S:的鉻組分是以碩化鉻形式存在。 9. 如申請專利範圍第8項之熱噴塗覆底材，其中該塗層含有至少一種選自銪、鑭、矽、給、铈、鐙、钒、鈮、鈦、鎢、鉅和鉻的元素；其中該元素實質上是以碩化物形式存在。 -2- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 493015 經濟部中央標準局員工消費合作社印製 A8 B8 C8 D8 、申請專利範圍 10.如申請專利範圍第8項之熱噴塗覆底材，其中該底材係選自鈦、綱、鋁、鎳、鈷及其合金。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)A8 B8 C8 D8 Bulletin No. 84106453 "A Method for Preparing Carbide Particles Dispersed in Metal Chromium Aluminum Yttrium-Based Coatings" Patent Amendment (November 1987) (Fill in this page again) 1. A method of preparing MCrA1Y-based anti-oxidation and corrosion coatings selected from the group consisting of iron, cobalt, nickel, and mixtures thereof, which comprises using a gaseous fuel-gasifier mixture by a detonation gun A device for thermally spraying a MCrA 1Y-based powder composition onto the surface of a substrate. The gas-fuel mixture includes an oxidant and at least one combustible gas selected from saturated and unsaturated hydrocarbons, wherein the atomic ratio of the gas to the atom is 1.044: 1 To 1 state 0: 1; and the masterpiece in the gaseous fuel-gasifier is sufficient to convert 30-80 weight S: the chromium component in the coating to master chromium; and the master exists in at least the coating 1% by weight. 2. The method according to item 1 of the patent application, wherein the coated substrate is heated to a temperature above 800TC for a heating time sufficient to stabilize the reaction between the master in the fuel-oxidant mixture and the chromium in the powder composition to produce the required amount Sulfonated chromium. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 3. As in the method of applying for the scope of patent No. 1, the MCrAlY-based powder composition further comprises at least one selected from the group consisting of scandium, lanthanum, silicon, hafnium, giant, tungsten, titanium, zirconium Elements of rhenium, hafnium, niobium, vanadium, and hafnium. 4. The method according to item 1 of the scope of patent application, wherein the combustible gas is a mixture of acetylene and propylene; the atomic ratio of oxygen to sulphur is 1.02: 1 to 1.00: 1, and the weight of the coating is 40-80 The chromium component is sulfonated chromium. -1- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 493015 A8 B8 C8 D8 Six. Application for patent scope 5. — Preparation of MCrAlY based on iron, cobalt, nickel and mixtures thereof A method for anti-gasification and corrosion coating, which conventionally includes thermally spraying a MCrAlY-based powder composition on the surface of a substrate by using a gas fuel-gasifier mixture through a high-speed gas fuel device. The gas fuel-gasifier mixture includes An oxidant and at least one combustible gas selected from saturated and unsaturated hydrocarbons, wherein the ratio of oxygen to fuel is 4: 1 to 1: 1 in cubic feet per hour, and the coating contains 30-7 5 weight S; The composition of chromium in the form of chrome. 6. The method according to item 5 of the patent application, wherein the coated substrate is heated to a temperature of 800 ¾ or more, and the heating time is sufficient to stabilize the reaction between the sulfur in the fuel-gasifier mixture and the chromium in the powder composition to form The required amount of chromium carbide. 7. The method according to item 5 of the patent application, wherein the MCrAlY-based powder composition further contains at least one element selected from the group consisting of scandium, lanthanum, silicon, osmium, giant, junction, tungsten, vanadium, hafnium, niobium, and mirror. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) 8. — A substrate coated with a thermal spray coating including MCrAlY-based materials, where M is selected from iron, cobalt, Nickel and mixtures thereof, in which 30-80% by weight of the S: chromium component is present in the form of master chromium. 9. The thermal spray coating substrate according to item 8 of the patent application, wherein the coating contains at least one element selected from the group consisting of scandium, lanthanum, silicon, silicon, cerium, thorium, vanadium, niobium, titanium, tungsten, giant and chromium ; Where the element is essentially in the form of a master compound. -2- This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 493015 Printed by A8 B8 C8 D8 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, and the scope of patent application 10. Such as the heat of the patent application item No. 8 Spray coated substrate, wherein the substrate is selected from the group consisting of titanium, steel, aluminum, nickel, cobalt, and alloys thereof. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)